CN106082261B - A kind of Ti MWW molecular sieves and preparation method thereof - Google Patents
A kind of Ti MWW molecular sieves and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Ti MWW molecular sieves and preparation method thereof, first synthesize the water silicon sodium stone of the two-dimensional structure of the Ti containing four-coordination, three-dimensional structure MWW type Ti MWW molecular sieves are then converted it under hydrothermal synthesizing condition；Reactant mixture preparation process is simple, it is not necessary to introduces boron source as crystallization promoting agent, it is not required that the step of removing boron with pickling post-processing approach, it is not required that and mixing plastic is carried out respectively, simplifies operating procedure, is easily controlled, it is reproducible；This method production procedure is short, and cost is low, is advantageous to industrialized production and application；This method crystallization time is short, and template dosage can substantially reduce, and it is few the defects of cell configuration and cause there is very high hydrophobicity and oxidation susceptibility.The Ti MWW molecular sieves of synthesis comprise only Si and Ti crystallizations, containing minimal amount of non-skeleton Ti, do not contain A1, have that relative crystallinity is high, and fault of construction is few, and heat endurance is high, the characteristics of very high hydrophobicity and oxidation susceptibility and nanocrystal yardstick.
Description
Technical field
The present invention relates to a kind of Ti-MWW molecular sieves and preparation method thereof, belong to inorganic chemical synthesis technical field.
Background technology
Ti-MWW molecular sieves are probably maximally effective titanium-silicon molecular sieve catalyst in current epoxidation reaction of olefines, i.e., mistake
Cross metal titanium atom and introduce MWW framework of molecular sieve, Ti-MWW molecular sieves are formed, at first in Chemistry Letters (Chemistry
Letters, 2000,774) disclosure report.Compared with TS-1, MWW HTSs possess the advantages of following unique：(1) produce
Relative inexpensiveness, preparation method are varied；(2) structure plasticity of stratiform presoma is strong, a variety of methods can be used to adjust
Become and modify, there is more open pore passage structure；(3) in various types of olefins or the oxidation reaction of Isosorbide-5-Nitrae-dioxane, Ti-
MWW shows more high catalytic activity, and in ketone Ammoximation reaction, the selectivity of oxime is higher, in benzothiophene or dibenzo
In the oxidation reaction of thiophene, there is more preferable catalytic effect.
The process of direct Hydrothermal Synthesiss Ti-MWW molecular sieves is because the hydrolysis of alkoxide of titanium strongly generates substantial amounts of
Non-skeleton Ti species, these can directly affect the Ti-MWW molecular sieve catalytic oxidation susceptibilities of synthesis, and using dealuminzation MWW zeolites as
The activated centre of the acidic hydrophilic of the synthetic method member-retaining portion of crystal seed, this can also influence Ti-MWW molecular sieve catalytic oxidisability
Energy.In addition, more cell configuration defect be present and stability and hydrophobicity are poor, template dosage in the Ti-MWW molecular sieves of synthesis
It is excessive and cost is too high, the diffusion that larger crystal grain is unfavorable for reactant molecule is generated, these are all direct hydrothermal synthesis method institutes
The problem of bringing.Comparatively speaking, report Ti-MWW preparation sides in Chemistry Letters (Chemistry Letters, 2000,774)
The characteristics of method is main is to introduce boron source as crystallization promoting agent, and gel synthetic crystallization degree under hydrothermal conditions is formed with titanium source and silicon source
Higher Ti-MWW structure molecular screens.Most of boron atom does not enter into framework of molecular sieve, because the Si/B in product is 11
To in the range of 14, and if reducing the dosage of boric acid when feeding intake, Ti-MWW just can not complete crystallization.This shows to add in gel
Excessive boric acid is essential, but final boron atom does not enter into framework of molecular sieve, but leaves system into filtrate.Institute
So that from economic considerations, this is to cause very big wastage of material.Although into the Boron contents of framework of molecular sieve far fewer than crystallization mistake
In journey, but the boron in skeleton can produce weak Bronsted acid, add the electronegativity of Ti-MWW framework of molecular sieve, finally
Activated centre Ti (IV) catalytic performance, and the selectivity of reaction principal product will be influenceed in catalytic reaction.Therefore need by
Ti-MWW molecular screen primary powders handle certain time at a set temperature with finite concentration and a certain amount of acid solution, last fired
Obtain product Ti-MWW molecular sieves.The above method obtains product Ti-MWW molecular sieves, but the method process is complicated, technological process
Long, production cost is high, is unfavorable for industrialized production and application.
CN1466545A discloses a kind of production method of titanosilicate catalyst, and by using this catalyst
Oxidation reaction production oxidized compound method, preparation process same Chemistry Letters substantially (Chemistry Letters, 2000：
7740) method, the defects of similar be present.Document (Catalysis Surveys from Asia, 2004,8 (2):137) report
Road, Ti-MWW molecular sieves are maximally effective titanium-silicon molecular sieve catalysts in current epoxidation reaction of olefines, but need to be developed simpler
Single preparation method is in favor of the application of the molecular sieve.CN1686795A discloses an a kind of step into composing Ti-MWW molecular sieves
Method, preparation process is：Silicon source, titanium source, boron source, template, Fluorine source and water are uniformly mixed into glue, hydrothermal crystallizing 5 hours
~20 days, obtain Ti-MWW molecular screen primary powders；This synthetic method process is relatively easy, but needs to add Fluorine source, both adds cost,
The corrosivity to equipment is added again.CN101012062A discloses one kind and introduces surface during Ti-MWW Crystallization of Zeolite
Activating agent, 3~10 days methods for preparing Ti-MWW molecular screen primary powders of hydrothermal crystallizing；The addition of surfactant improves catalyst
Activity, but also increase production cost, while crystallization time length adds energy resource consumption and production cost.W003/
074421A1 discloses a kind of titan silicate, and composition structural formula is：XTiO2 (1-x) SiO2, there is the X- of MWW structure molecular screens
X ray diffraction spectrogram；Its preparation process：First hydrothermal crystallizing prepares siliceous, boron MWW structured forerunners, and then, acid treatment obtains
MWW structured forerunners, then the product that upper step obtains is subjected to hydrothermal crystallizing processing together with titanium source and the template aqueous solution, most
The fired titan silicate product for obtaining crystal structure of product that upper step is obtained afterwards；The synthetic method of the patent has been carried out twice
Hydrothermal crystallization process, technological process length, cost are high.CN104944436A provides a kind of side of Fast back-projection algorithm Ti-MWW molecular sieves
Method, this method are characterized mainly in that organic amine, water, titanium source, boron source and silicon source uniformly are mixed and made into gel by a mole composition puts
Enter closed reactor to carry out rotating ageing around horizontal rotating shaft and rotate crystallization, molecular sieve crystalline flour is obtained, by the post processing of some
Finally give Ti-MWW zeolite products；The patent synthetic method is difficult to the high-crystallinity that crystallization obtains high skeleton Ti contents completely
Zeolite product, substantial amounts of Ti is in outside skeleton, the density in Ti-MWW molecular sieves activated centre is reduced, in addition, the synthesis
Method is higher for equipment requirement, it is difficult to which industry amplification synthesis, integrated cost are higher.
Understand that, it is necessary to introduce boron source as crystallization promoting agent, acid treatment is used in synthesizing afterwards from synthetic method presented above
Boron is removed to ensure the activity of Ti-MWW molecular sieves, Ti-MWW Zeolite synthesis is complex, causes technological process to grow, and is produced into
This height, it is unfavorable for industrialized production and the application of the molecular sieve.
The content of the invention
The technical problems to be solved by the invention are to be directed to the deficiencies in the prior art, and provide a kind of Ti-MWW points
Son sieve, the molecular sieve have MWW skeleton structures, comprise only Si and Ti crystallizations, substantially free of Al, contain minimal amount of non-skeleton
Ti。
The second object of the present invention is to provide a kind of preparation method of above-mentioned Ti-MWW molecular sieves, first synthesizes Ti containing four-coordination
Two-dimensional structure water silicon sodium stone (kanemite), three-dimensional structure MWW types Ti- is then converted it under hydrothermal synthesizing condition
MWW molecular sieves；Boron source need not be introduced during synthesis Ti-MWW molecular sieves, crystallization time is short, and template dosage can be significantly
Reduce, and it is few the defects of cell configuration and cause there is very high hydrophobicity and oxidation susceptibility, bigger molecule body can be used as
The excellent epoxidation catalyst of product alkene.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of preparation method of Ti-MWW molecular sieves, comprises the following steps：
(1) esters of silicon acis, titanate esters and butanol are well mixed, then add NaOH and H thereto2O, then room temperature~
It is sufficiently stirred at 120 DEG C and is prepared into mixed solution；By described mixed solution at 650~750 DEG C in closed pressure vessel
3~6h is reacted, product obtains the water silicon sodium stone (kanemite) containing Ti after filtration, washing and drying after completion of the reaction；
Described esters of silicon acis is with SiO2Meter, titanate esters are with TiO2Meter, NaOH are with Na2O is counted, SiO2：TiO2：Butanol：Na2O：
H2O mol ratio=1：0.01~0.05：4.0~15.0：0.015~0.15：4.5~35.0；
(2) by the water silicon sodium stone obtained in step (1) and template and H2After O is well mixed, in reactor, 120
Crystallization 2~15 days at~170 DEG C, obtain the HTS original powder with MWW skeleton structures；
Described water silicon sodium stone is with SiO2Meter, SiO2：Template：H2O mol ratio=1：0.1~1.0：2.0~8.0；
(3) by the HTS original powder obtained in step (2) and aqueous acid according to 1：5~100 weight is than mixing
Reactant mixture uniformly is prepared into, reactant mixture reacts 0.5~24h at room temperature~100 DEG C, and product passes through after completion of the reaction
Filter, washing, obtain acid-treated product after drying；
(4) acid-treated product that step (3) obtains is obtained into Ti-MWW molecules in 500~600 DEG C of roasting 2~l0 hours
Sieve.
In above-mentioned technical proposal, in step (1), described esters of silicon acis is tetraethyl orthosilicate, quanmethyl silicate, the fourth of silicic acid four
Any one in ester, preferably any one in quanmethyl silicate, tetraethyl orthosilicate.
In above-mentioned technical proposal, in step (1), described titanate esters are tetraethyl titanate, tetraisopropyl titanate or metatitanic acid
Any one in four butyl esters, preferably butyl titanate.
In above-mentioned technical proposal, in step (1), described butanol is any one in the tert-butyl alcohol or n-butanol, or
The two mixture mixed with arbitrary proportion.
In above-mentioned technical proposal, in step (1), described SiO2：TiO2：Butanol：Na2O：H2O mol ratio is preferably 1：
0.0125~0.033：4.0~8.0：0.026~0.052:6.5~13.5.
In above-mentioned technical proposal, in step (2), described template be hexamethylene imine, piperidines, N, N, N- front threes
In base -1- adamantane ammonium hydroxide any one, the mixture that is mixed with arbitrary proportion of two kinds and the above.
In above-mentioned technical proposal, in step (3), sour concentration is 0.1~1.0mo1/L in described aqueous acid.
In above-mentioned technical proposal, in step (3), described aqueous acid is the aqueous solution of inorganic acid or organic acid, its
In, described inorganic acid is any one in hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, and described organic acid is formic acid, acetic acid, third
Acid or tartaric acid in any one.
In above-mentioned technical proposal, in step (3), described aqueous acid is preferably the aqueous solution of inorganic acid or organic acid
The product obtained after 5~24h is heat-treated at 70~100 DEG C.
In above-mentioned technical proposal, in step (3), the weight ratio of described HTS original powder and aqueous acid is preferably
1：10~50.
The present invention also provides a kind of Ti-MWW molecular sieves being prepared by the above method, and the molecular sieve belongs to typical
MWW structures, XRD are as shown in Figure 1.
Compared with prior art, the present invention has following remarkable advantage:
(1) during preparing Ti-MWW molecular screen primary powders, reactant mixture preparation process is simple, it is not necessary to introduces boron source work
For crystallization promoting agent, it is not required that the step of removing boron with pickling post-processing approach, it is not required that carry out mixing plastic respectively, simplify
Operating procedure, is easily controlled, reproducible；
(2) production procedure is short, and cost is low, is advantageous to industrialized production and application.
Brief description of the drawings：
Fig. 1：The XRD spectrum for the Ti-MWW molecular sieves that the embodiment of the present invention 1 obtains.
Embodiment
The embodiment of technical solution of the present invention is described in detail below, but the present invention is not limited in following description
Hold：
Embodiment 1：
(1) by 212.58g silester (with SiO2Meter), 17.19g butyl titanates are (with TiO2Meter) and the tertiary fourths of 229.47g
Alcohol is well mixed, and 3.58g NaOH solids are then slowly added dropwise thereto under the situation being stirred continuously (with Na2O is counted) and
118.0gH2O, then it is sufficiently stirred at room temperature and is prepared into mixed solution；By mixed solution in 700 DEG C of closed pressure vessels
4h is reacted, slurries are filtered to, washed simultaneously 120 DEG C of drying Ti containing four-coordination two-dimensional layer water silicon sodium stone powders after completion of the reaction；
SiO2：TiO2：Butanol：Na2O：H2O mol ratio=1：0.05：4.0：0.043：6.6；
(2) by the water silicon sodium stone obtained in step (1) (with SiO2Meter) with 22.54g hexamethylene imines (HMI) and
39.60g H2After O is well mixed, in reactor, at 140 DEG C crystallization 4 days, obtain Ti-MWW molecular screen primary powders；
SiO2：Hexamethylene imine：Mol ratio=1 of water：0.16：2.2；
(3) by the HTS original powder and 0.4mol/L acetic acid aqueous solution that are obtained in step (2) according to 1：50 weight
Amount ratio is prepared into reactant mixture, handle 2 hours at 90 DEG C, after completion of the reaction product again by filtering, wash, 120 DEG C do
It is dry to obtain acid-treated product；
(4) acid-treated product that step (3) obtains is obtained into Ti-MWW sieve sample 1# in 3 hours in 550 DEG C of roastings, its
XRD spectrum is as shown in Figure 1：In figure, the molecular sieve has θ=7.22 ° of characteristic peak 2,7.90 °, 9.54 °, 14.42 °, 16.14 °,
22.64 °, 23.72 °, 26.14 °, belong to typical MWW structures.
The average grain diameter and relative crystallinity for the sample that measure embodiment 1 obtains；And crystallization reservation degree is calculated, crystallization retains
Spend ratio for relative crystallinity after roasting Template removal and initial sample relative crystallinity；Single-autoclave yield rate is determined, using ICP's
Al content in method analyzing molecules sieve, what is obtained the results are shown in Table 1.
Embodiment 2：
(1) by 155.33g methyl silicates (with SiO2Meter), 8.59g butyl titanates are (with TiO2Meter) and the tertiary fourths of 449.21g
Alcohol is well mixed, and 2.17g NaOH solids are then slowly added dropwise thereto under the situation being stirred continuously (with Na2O is counted) and
142.2g H2O, then it is sufficiently stirred at room temperature and is prepared into mixed solution；By mixed solution in 650 DEG C of closed pressure vessels
5h is reacted, slurries are filtered to, washed simultaneously 120 DEG C of drying Ti containing four-coordination two-dimensional layer water silicon sodium stone powders after completion of the reaction；
SiO2：TiO2：Butanol：Na2O：H2O mol ratio=1：0.025：6.0：0.026：7.9；
(2) by the water silicon sodium stone obtained in step (1) (with SiO2Meter) with 45.08g hexamethylene imines (HMI) and
64.80g H2After O is well mixed, in reactor, at 150 DEG C crystallization 5 days, obtain Ti-MWW molecular screen primary powders；
SiO2：Hexamethylene imine：Mol ratio=1 of water：0.32：3.6；
(3) by the HTS original powder and 0.2mol/L aqueous hydrochloric acid solution that are obtained in step (2) according to 1：70 weight
Amount ratio is prepared into reactant mixture, handle 3 hours at 95 DEG C, after completion of the reaction product again by filtering, wash, 115 DEG C do
It is dry to obtain acid-treated product；
(4) acid-treated product that step (3) obtains is obtained into Ti-MWW sieve samples 2# in 4 hours in 540 DEG C of roastings.
The average grain diameter of the sample obtained according to the methods described of embodiment 1 measure embodiment 2, relative crystallinity, crystallization are protected
Office Copy, single-autoclave yield rate and Al content, the results are shown in Table 1.
Embodiment 3：
(1) by 212.58g silester (with SiO2Meter), 3.84g tetraethyl titanates are (with TiO2Meter) and the tertiary fourths of 598.95g
Alcohol is well mixed, and 2.75g NaOH solids are then slowly added dropwise thereto under the situation being stirred continuously (with Na2O is counted) and
212.40g H2O, then it is sufficiently stirred at room temperature and is prepared into mixed solution；By mixed solution in 750 DEG C of closed pressure vessels
Middle reaction 4h, slurries are filtered to, washed simultaneously 120 DEG C of drying Ti containing four-coordination two-dimensional layer water silicon sodium stone flours after completion of the reaction
End；
SiO2：TiO2：Butanol：Na2O：H2O mol ratio=1：0.0167：8.0：0.033：11.8；
(2) by the water silicon sodium stone obtained in step (1) (with SiO2Meter) (PI, mass concentration are with 100.29g piperidines
And 95.40g H 45%)2After O is well mixed, in reactor, at 170 DEG C crystallization 3 days, obtain Ti-MWW molecular screen primary powders；
SiO2：Piperidines：Mol ratio=1 of water：0.53：8.0；
(3) by the HTS original powder and 0.7mol/L aqueous solution of nitric acid that are obtained in step (2) according to 1：30 weight
Amount ratio is prepared into reactant mixture, handle 5 hours at 85 DEG C, after completion of the reaction product again by filtering, wash, 120 DEG C do
It is dry to obtain acid-treated product；
(4) acid-treated product that step (3) obtains is obtained into Ti-MWW sieve samples 3# in 4 hours in 550 DEG C of roastings.
The average grain diameter of the sample obtained according to the methods described of embodiment 1 measure embodiment 3, relative crystallinity, crystallization are protected
Office Copy, single-autoclave yield rate and Al content, the results are shown in Table 1.
Embodiment 4
(1) by 155.33g methyl silicates (with SiO2Meter), 2.87g tetraisopropyl titanates are (with TiO2Meter) and uncle 973.29g
Butanol is well mixed, and 4.33g NaOH solids are then slowly added dropwise thereto under the situation being stirred continuously (with Na2O is counted) and
464.40g H2O, then it is sufficiently stirred at room temperature and is prepared into mixed solution；By mixed solution in 700 DEG C of closed pressure vessels
Middle reaction 5h, slurries are filtered to, washed simultaneously 120 DEG C of drying Ti containing four-coordination two-dimensional layer water silicon sodium stone flours after completion of the reaction
End；
SiO2：TiO2：Butanol：Na2O：H2O mol ratio=1：0.01：13.0：0.052：25.8；
(2) by the water silicon sodium stone obtained in step (1) (with SiO2Meter) and 769.31g N, N, N- trimethyl -1- adamantane
Ammonium hydroxide (TMDadOH, 25% mass concentration) and 142.20g H2After O is well mixed, in reactor, brilliant at 140 DEG C
Change 7 days, obtain Ti-MWW molecular screen primary powders；
SiO2：N, N, N- trimethyl -1- adamantane ammonium hydroxide：Mol ratio=1 of water：0.91：7.9；
(3) by the HTS original powder and 0.6mol/L aqueous tartaric acid solution that are obtained in step (2) according to 1：20
Weight ratio is prepared into reactant mixture, is handled at 90 DEG C 3 hours, product is again by filtering, washing, 120 DEG C after completion of the reaction
It is dried to obtain acid-treated product；
(4) acid-treated product that step (3) obtains is obtained into Ti-MWW sieve samples 4# in 5 hours in 540 DEG C of roastings.
The average grain diameter of the sample obtained according to the methods described of embodiment 1 measure embodiment 4, relative crystallinity, crystallization are protected
Office Copy, single-autoclave yield rate and Al content, the results are shown in Table 1.
Comparative example
At room temperature, a certain amount of hexamethylene imine (HMI) is added in a certain amount of water, after stirring half an hour, then according to
Secondary addition butyl titanate is (with TiO2Meter), boric acid is (with B2O3Meter) and a certain amount of white carbon is added (with SiO after stirring2
Meter), reaction gel is made, gel mole composition is SiO2：0.04TiO2：0.67B2O3：1.5HMI：25.0H2O.
Then reaction gel is placed in closed reactor, closed reactor is fixed on the water of homogeneous reactor by connecting rod
On flat turn axle, regulation slewing rate is 10 revs/min.First it is aged 12 hours at 80 DEG C, then adjusts slewing rate as 30 revs/min
Clock, it is aged 12 hours at 120 DEG C, then adjusts slewing rate as 40 revs/min, in 170 DEG C of crystallization 30 hours, then adjusts rotation speed
Rate is 60 revs/min, in 170 DEG C of crystallization 30 hours, filtered, washing, dries, obtains Ti-MWW molecular screen primary powders.It will obtain
Molecular screen primary powder and concentration be that 1.0mol/L aqueous solution of nitric acid is 1 by weight：50 mixing, flow back 20 hours at 80 DEG C, warp
Filtering, washing, dry, obtain acid-treated product；Acid-treated product is calcined 8 hours in 550 DEG C again, obtains Ti-MWW points of product
Son sieve.
The performance of Ti-MWW molecular sieves prepared by 1 different embodiments of table
| Detection project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example |
| Relative crystallinity/% | 98.1 | 95.9 | 95.4 | 99.8 | 78.3 |
| Average grain size/nm | 46 | 55 | 58 | 49 | 109 |
| Single-autoclave yield rate/% | 78.9 | 76.8 | 72.5 | 77.4 | 46.6 |
| Crystallize reservation degree/% | 91.2 | 90.8 | 91.4 | 92.2 | 73.3 |
| Al content (ICP measure) | <1ppm | <2ppm | <1ppm | <2ppm | >10ppm |
| B content (ICP measure) | <1ppm | <1ppm | <1ppm | <1ppm | >100ppm |
| Infrared spectrum 960cm-1Locate feature peak intensity | By force | By force | By force | By force | It is weak |
As shown in Table 1：Infrared spectrum 960cm-1Locate the characteristic absorption that characteristic peak is four-coordination Ti in sieve sample skeleton
Peak, the power at this feature peak illustrates the relative prevalence of skeleton Ti contents, if peak intensity is high, illustrates that skeleton Ti contents are more,
And non-skeleton Ti is less.From table 1, the molecular sieve infrared spectrum 960cm prepared using method provided by the invention-1Locate feature
The intensity at peak is stronger, and its skeleton Ti content is higher.Al content illustrates to be substantially free of in sintetics below Monitoring lower-cut
Al.Contrastingly, the Ti-MWW molecular sieves synthesized using comparative example, may introduce more Al impurity, while can not have
Effect removing B element, skeleton Ti contents are relatively fewer, and all than relatively low, each side refers to obtained relative crystallinity and reservation crystallinity
Mark is worse than the physical and chemical performance of product of the embodiment of the present invention.
Examples detailed above is technical concept and technical characterstic to illustrate the invention, can not limit the present invention's with this
Protection domain.The equivalent transformation or modification that all essence according to the present invention is done, should all cover in protection scope of the present invention
Within.
Claims (10)
1. a kind of preparation method of Ti-MWW molecular sieves, it is characterised in that comprise the following steps：
(1) esters of silicon acis, titanate esters and butanol are well mixed, then add NaOH and H thereto2O, then at room temperature~120 DEG C
It is sufficiently stirred and is prepared into mixed solution；Described mixed solution is reacted into 3~6h at 650~750 DEG C in closed pressure vessel,
Product obtains the water silicon sodium stone containing Ti after filtration, washing and drying after completion of the reaction；
Described esters of silicon acis is with SiO2Meter, titanate esters are with TiO2Meter, NaOH are with Na2O is counted, SiO2：TiO2：Butanol：Na2O：H2O's rubs
That ratio=1：0.01~0.05：4.0~15.0：0.015~0.15：4.5~35.0；
(2) by the water silicon sodium stone obtained in step (1) and template and H2After O is well mixed, in reactor, 120~170
Crystallization 2~15 days at DEG C, obtain the HTS original powder with MWW skeleton structures；
Described water silicon sodium stone is with SiO2Meter, SiO2：Template：H2O mol ratio=1：0.1~1.0：2.0~8.0；
(3) by the HTS original powder obtained in step (2) and aqueous acid according to 1：5~100 weight is than well mixed
Be prepared into reactant mixture, reactant mixture reacts 0.5~24h at room temperature~100 DEG C, after completion of the reaction product it is filtered,
Washing, obtain acid-treated product after drying；
(4) acid-treated product that step (3) obtains is obtained into Ti-MWW molecular sieves in 500~600 DEG C of roasting 2~l0 hours.
2. according to the method for claim 1, it is characterised in that in step (1), described esters of silicon acis be tetraethyl orthosilicate,
Any one in quanmethyl silicate, the butyl ester of silicic acid four；Described titanate esters are tetraethyl titanate, tetraisopropyl titanate or metatitanic acid
Any one in four butyl esters；Described butanol is any one in the tert-butyl alcohol or n-butanol, or the two is with arbitrary proportion
The mixture mixed.
3. according to the method for claim 2, it is characterised in that described esters of silicon acis is quanmethyl silicate, tetraethyl orthosilicate
In any one, described titanate esters are butyl titanate.
4. according to the method for claim 1, it is characterised in that in step (1), described SiO2：TiO2：Butanol：Na2O：
H2O mol ratio is 1：0.0125~0.033：4.0~8.0：0.026~0.052:6.5~13.5.
5. according to the method for claim 1, it is characterised in that in step (2), described template is that hexa-methylene is sub-
Amine, piperidines, N, N, in N- trimethyl -1- adamantane ammonium hydroxide any one, two kinds and the above so that arbitrary proportion mixes and
Into mixture.
6. according to the method for claim 1, it is characterised in that in step (3), described aqueous acid be inorganic acid or
The aqueous solution of organic acid, sour concentration is 0.1~1.0mo1/L in aqueous acid.
7. according to the method for claim 6, it is characterised in that described inorganic acid is in hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid
Any one, described organic acid be formic acid, acetic acid, propionic acid or tartaric acid in any one.
8. according to the method for claim 6, it is characterised in that described aqueous acid is the water of inorganic acid or organic acid
Solution is heat-treated the product obtained after 5~24h at 70~100 DEG C.
9. according to the method for claim 1, it is characterised in that in step (3), described HTS original powder and sour water
The weight ratio of solution is 1：10~50.
10. a kind of Ti-MWW molecular sieves, it is characterised in that be prepared by any one of claim 1~9 methods described
's.
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